CN105498767B - For synthesizing the catalyst of 3 acetoxyl group propionic aldehyde - Google Patents
For synthesizing the catalyst of 3 acetoxyl group propionic aldehyde Download PDFInfo
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Abstract
The present invention relates to the catalyst for synthesizing 3 acetoxyl group propionic aldehyde, mainly solve the problems, such as that the catalyst activity and selectivity of 3 acetoxyl group propionic aldehyde in the prior art is relatively low, by using the catalyst of 3 acetoxyl group propionic aldehyde, the catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkaline-earth metal and the technical scheme selected from least one of VA and IVB metallic element, the technical problem is preferably resolved, in the industrial production available for 1.3 propane diols.
Description
Technical field
The present invention relates to the catalyst for synthesizing 3- acetoxyl group propionic aldehyde, the production method and 3- second of the catalyst
The synthetic method of acyloxy propionic aldehyde.
Background technology
1.3- propane diols (1.3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, detergent, preservative,
The synthesis of emulsifying agent, it is also used for the industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its
Most important purposes is as monomer and the polytrimethylene terephthalate (PTT) of terephthalic acid (TPA) synthesizing new polyester material one.
The preparation method of 1.3- propane diols has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehyde
Stiasny method, acrylic acid ester process, bioanalysis, vinyl acetate hydroformylation etc..At present, 1.3-PDO industrialized preparing process
For chemical synthesis, international market is mainly by German Degussa companies, shell Shell companies of the U.S. and du pont company three
Family's monopolization.Degussa companies are using acrolein hydration hydrogenation method (AC methods), Shell Co. Ltd using oxirane carbonyl
The thorugh biologic engineering method (MF methods) that change method (EO methods), E.I.Du Pont Company innovate using oneself.Its ethylene oxide two-step process
It is current prevailing technology with acrolein hydration method technique.
It is well known that there is a carbon-carbon double bond in vinyl acetate, hydroformylation reaction can occur for the key, the one of double bond
An aldehyde radical is added on individual carbon atom, generates the isomer of acetoxyl group propionic aldehyde.The aldehyde can become hydroxyl by hydrogenation
Base, ester group can be become hydroxyl by hydrolysis and form glycol, and such vinyl acetate is by hydroformylation, hydrogenation and hydrolysis can
Prepare 1.3- propane diols.
Taught in the patents such as patent US4072709 (Production of lactic acid) and utilize vinyl acetate
It is catalyst by using homogeneous rhodium compound or propionate is raw material, by hydroformylation reaction, obtains α-acetyl oxygen
Base propionic aldehyde or α-propionyloxy propionic aldehyde.Whether separation or not, then obtains 1.3-PDO by hydrogenation and hydrolytic process, or
Oxidation and hydrolysis obtain lactic acid.But there are 3- acetoxyl groups propionic aldehyde receipts in the above method during 3- acetoxyl group propionic aldehyde is prepared
The problem of rate is low and selective not high.
The content of the invention
The problem of one of technical problems to be solved by the invention are that 3- acetoxyl group propionic aldehyde yields are low and selectivity is low, carries
For a kind of catalyst for being used to synthesize 3- acetoxyl group propionic aldehyde, the catalyst has 3- acetoxyl group propionic aldehyde high incomes to 3- acetyl
The characteristics of epoxide propionic aldehyde is selectively high.
The two of the technical problems to be solved by the invention are the producers using one of the above-mentioned technical problem catalyst
Method.
The three of the technical problems to be solved by the invention are the 3- acetyl using one of the above-mentioned technical problem catalyst
The synthetic method of epoxide propionic aldehyde.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：For synthesizing 3- acetoxyl groups
The catalyst of propionic aldehyde, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkaline earth gold
Belong to and selected from least one of VA and IVB metallic element.It is preferred that the active component includes rhodium, alkaline-earth metal, is selected from simultaneously
At least one of VA metallic elements and selected from least one of IVB metallic elements.Now VA metallic element and IVB gold
Have between category element in terms of 3- acetoxyl groups propionic aldehyde selectivity and yield is improved and act synergistically.
In above-mentioned technical proposal, the alkaline-earth metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium.
In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.
In above-mentioned technical proposal, the IVB metals preferably are selected from least one of titanium, zirconium and hafnium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including rhodium metal element, alkali
Earth metal, VA metallic elements and IVB metallic elements；Such as the active component is made up of rhodium, strontium, antimony and hafnium, or by rhodium,
Strontium, antimony, bismuth and hafnium composition, are either made up of or by rhodium, strontium, beryllium, antimony, bismuth, hafnium and titanium group rhodium, strontium, antimony, bismuth, hafnium and titanium
Into.
In above-mentioned technical proposal, the content of rhodium is preferably 3.00~15.00g/L in the catalyst, and more preferably 5.00
~10.00g/L；The content of alkaline-earth metal is preferably 0.10~3.00g/L in the catalyst, more preferably 0.50~3.00g/
L；In the catalyst selected from VA and IVB at least one content of metal be preferably 0.10~5.00g/L, more preferably
1.00~5.00g/L.Load surface area per unit volume used in the catalyst is preferably 50~300m2/ g, more preferably 150~200m2/
G, pore volume are preferably 0.80~1.20, and more preferably 0.90~1.00.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The production method of catalyst described in case, comprises the following steps：
1. by catalyst composition by the solution of metallic compound in rhodium compound, alkaline earth metal compound, VA and IVB with
Carrier mixes；
2. dry.
In above-mentioned technical proposal, 1. the rhodium compound preferably is selected from rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate step
At least one；1. the alkaline earth metal compound preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkaline earth gold to step
At least one of genus nitrobacter, alkali earth metal sulfate and Alkaline Earth Metal Acetate；1. the VA metallic compounds are excellent for step
Select at least one of basic bismuth carbonate, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate and antimony chloride；Step 1. institute
Metallic compound in IVB is stated preferably to be selected from titanium tetrachloride, ammonium titanium fluoride, hexafluorotitanic acid, zirconium chloride, acetic acid zirconium and oxychloride hafnium
It is at least one；2. the drying temperature is 80~120 DEG C, more preferably 100~120 DEG C to step.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of 3- acetoxyl group propionic aldehyde,
Using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent, the reaction generation 3- in the presence of catalyst and accelerator
Acetoxyl group propionic aldehyde.At least one of the preferred pyridine of the accelerator and triphenyl phosphorus.
The key of the present invention is the selection of catalyst, and skilled person will know how suitable according to determination is actually needed
Reaction temperature, the reaction time, the proportioning of reaction pressure and material.But the temperature reacted in above-mentioned technical proposal is preferably
50~180 DEG C；The pressure of reaction is preferably 1.0~15.0MPa；The time of reaction is preferably 1.0~15.0h.Carbon monoxide with
The mol ratio of hydrogen is preferably 0.10~10.0.
Product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), is pressed
Row formula calculates the conversion ratio of vinyl acetate and the yield and selectivity of 3- acetoxyl group propionic aldehyde：
Compared with prior art, key of the invention is that the active component of catalyst includes rhodium, alkaline-earth metal and is selected from
At least one of VA and IVB metallic element, be advantageous to improve the activity and stability of major catalyst, so as to improve 3- acetyl
The yield and selectivity of epoxide propionic aldehyde.
Test result indicates that using catalyst of the present invention, 3- acetoxyl group propionic aldehyde yield 85.31%, selectively reach
94.49%, achieve active component in preferable technique effect, especially catalyst while include rhodium, alkaline-earth metal, selected from VA
At least one of metallic element and during selected from least one of IVB metallic elements, achieve more prominent technique effect,
In industrial production available for 1.3- propane diols.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gSb3·3H2O、Sr(OAC)2·
0.5H2O and Cl3Sb, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Sb
Content 3.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.31%, and selectivity is 94.49%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 2】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gHf3·3H2O、Sr(OAC)2·
0.5H2O and oxychloride hafnium (HfOCl2·8H2O) it is sufficiently mixed and is dissolved in the water, obtain maceration extract 400ml, 1.0L is compared into surface
For 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Hf content
3.30g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.43%, and selectivity is 94.27%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：By the RhCl containing 6.50gRh and containing 2.00gSr3·3H2O and Sr (OAC)2·0.5H2O is abundant
Mixed dissolution obtains maceration extract 400ml in water, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm's
Spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.This is determined through ICP to urge
The Rh contents of agent are 6.50g/L, Sr contents 2.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 73.44%, and selectivity is 84.61%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Rh, Sr and Sb work
Property component and meanwhile performance of the catalyst performance ratio containing only Rh and Sr active constituent catalysts containing Rh, Sr and Hf active component will
More excellent, the selectivity and yield of 3- acetoxyl group propionic aldehyde will be high.
【Embodiment 3】
The preparation of catalyst：By the Rh (OAc) containing 6.50gRh, containing 2.00gMg and containing 3.30gSb3、MgSO4And Sb2O3Fill
Point mixed dissolution is in 8wt% aqueous solution of nitric acid in concentration, obtains maceration extract 400ml, than surface is 200m by 1.0L2/ g, hole
Hold for 1.00, a diameter of 5.6mm spherical Al2O3Carrier impregnation stands 3h in 80 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Mg contents 2.00g/L, Sb content 3.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.11%, and selectivity is 94.84%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 4】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gCa and containing 3.30gSb3·3H2O、Ca(NO3)2·
4H2O and Sb2(SO4)3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L
It is 150m than surface2/ g, pore volume 0.90, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in above-mentioned maceration extract
In 120 DEG C of dryings, the catalyst is obtained.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Ca content 2.00g/L,
Sb contents 3.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.71%, and selectivity is 94.21%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 5】
The preparation of catalyst：By the Rh containing 5.00gRh, containing 0.50gBe and containing 1.00gBi2(SO4)3·15H2O、BeCl2With
(BiO)2CO3·0.5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, hole
Hold for 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.The Rh contents that the catalyst is determined through ICP are 5.00g/L, Be contents 0.50g/L, Bi content 1.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 80.33%, and selectivity is 88.86%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 6】
The preparation of catalyst：By the RhCl containing 10.00gRh, containing 3.00gBa and containing 5.00gBi3·3H2O, BaO and BiCl3
It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtain maceration extract 400ml, than surface is 168m by 1.0L2/
G, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
To the catalyst.The Rh contents that the catalyst is determined through ICP are 10.00g/L, Ba contents 3.00g/L, Bi content 5.00g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.93%, and selectivity is 94.14%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 7】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gTi3·3H2O、Sr(OAC)2·
0.5H2O and ammonium titanium fluoride ((NH4)2TiF6) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, 1.0L is compared into surface
For 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Ti content
3.30g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.32%, and selectivity is 94.64%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 8】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gTi3·3H2O、Sr(OAC)2·
0.5H2O and hexafluorotitanic acid (H2TiF6) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, is than surface by 1.0L
168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Ti content
3.30g/L。
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.54%, and selectivity is 94.28%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 9】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gZr3·3H2O、Sr(OAC)2·
0.5H2O and ZrCl4It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume are
0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Zr content 3.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.37%, and selectivity is 94.36%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 10】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gZr3·3H2O、Sr(OAC)2·
0.5H2O and Zr (OAC)4It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g, hole
Hold for 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Zr content 3.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 0.2MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 1.0MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 50 DEG C, and the mol ratio of hydrogen and carbon monoxide is 1:After 10, sustained response 1.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 77.17%, and selectivity is 93.97%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 11】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gTi3·3H2O、Sr(OAC)2·
0.5H2O and TiCl4It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Ti
Content 3.30g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm, while agitating and heating is warming up to reaction temperature until pressure 15.0MPa
Degree, controlling reaction temperature are 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:After 1, sustained response 15.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 85.87%, and selectivity is 94.03%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 12】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr, containing 1.50gSb and containing 1.80gHf3·3H2O、
Sr(OAC)2·0.5H2O、Cl3Sb and oxychloride hafnium (HfOCl2·8H2O) it is sufficiently mixed the hydrochloric acid water for being dissolved in that concentration is 8wt%
In solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2
Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Rh of the catalyst is determined through ICP
Content is 6.50g/L, and Sr contents 2.00g/L, Sb content 1.50g/L, Hf content is 1.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 86.95%, and selectivity is 95.77%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, improve 3- acetoxyl group propionic aldehyde selectivity and
In terms of yield, in the catalyst that the present invention uses, there is synergy between VA metal Sb and IVB metals Hf.【Embodiment 13】
The preparation of catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr, containing 1.50gBi and containing 1.80gHf3·3H2O、
Sr(OAC)2·0.5H2O、BiCl3With oxychloride hafnium (HfOCl2·8H2O) it is sufficiently mixed the hydrochloric acid water for being dissolved in that concentration is 8wt%
In solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2
Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Rh of the catalyst is determined through ICP
Content is 6.50g/L, and Sr contents 2.00g/L, Bi content 1.50g/L, Hf content is 1.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 87.03%, and selectivity is 95.62%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 14】
The preparation of catalyst：By containing 6.50gRh, containing 2.00gSr, containing 0.50gSb, containing 1.00gBi and containing 1.80gHf's
RhCl3·3H2O、Sr(OAC)2·0.5H2O、Cl3Sb、BiCl3With oxychloride hafnium (HfOCl2·8H2O) be sufficiently mixed be dissolved in it is dense
Spend in the aqueous hydrochloric acid solution for 8wt%, obtain maceration extract 400ml, than surface be 168m by 1.0L2/ g, pore volume 0.94, diameter
For 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through
The Rh contents that ICP determines the catalyst are 6.50g/L, Sr contents 2.00g/L, Sb content 0.50g/L, Bi content 1.00g/L, Hf
Content is 1.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 88.75%, and selectivity is 96.47%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that the present invention uses, there is synergy in VA metals between Sb and Bi.
【Embodiment 15】
The preparation of catalyst：By containing 6.50gRh, containing 2.00gSr, containing 0.50gSb, containing 1.00gBi and containing 1.80gTi's
RhCl3·3H2O、Sr(OAC)2·0.5H2O、Cl3Sb、BiCl3With ammonium titanium fluoride ((NH4)2TiF6) be sufficiently mixed and be dissolved in concentration
Than surface it is 168m by 1.0L in 8wt% aqueous hydrochloric acid solution, to obtain maceration extract 400ml2/ g, pore volume 0.94 are a diameter of
5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP
The Rh contents for determining the catalyst are 6.50g/L, Sr contents 2.00g/L, Sb content 0.50g/L, Bi content 1.00g/L, and Ti contains
Measure as 1.80g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 88.53%, and selectivity is 96.67%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 16】
The preparation of catalyst：To contain 6.50gRh, containing 2.00gSr, containing 0.50gSb, containing 1.00gBi, containing 1.20gHf and contain
0.60gTi RhCl3·3H2O、Sr(OAC)2·0.5H2O、Cl3Sb、BiCl3, oxychloride hafnium (HfOCl2·8H2) and fluotitanic acid O
Ammonium ((NH4)2TiF6) be sufficiently mixed be dissolved in concentration be 8wt% aqueous hydrochloric acid solution in, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Sb
Content 0.50g/L, Bi content 1.00g/L, Hf content is 1.20g/L, and Ti contents are 0.60g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 89.84%, and selectivity is 97.55%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between IVB metals Ti, Hf, illustrate Rh, Sr, Sb,
Synergy well between six kinds of active components of Bi, Ti and Hf be present.
【Embodiment 17】
The preparation of catalyst：To contain 6.50gRh, containing 2.00gBe, containing 0.50gSb, containing 1.00gBi, containing 1.20gHf and contain
0.60gTi RhCl3·3H2O、BeCl2、Cl3Sb、BiCl3, oxychloride hafnium (HfOCl2·8H2) and ammonium titanium fluoride ((NH O4)2TiF6) be sufficiently mixed be dissolved in concentration be 8wt% aqueous hydrochloric acid solution in, obtain maceration extract 400ml, be than surface by 1.0L
168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Be contents 2.00g/L, Sb content
0.50g/L, Bi content 1.00g/L, Hf content are 1.20g/L, and Ti contents are 0.60g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 89.51%, and selectivity is 97.74%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
【Embodiment 18】
The preparation of catalyst：To contain 6.50gRh, containing 1.60gSr, containing 0.40gBe, containing 0.50gSb, containing 1.00gBi, contain
The 1.20gHf and RhCl containing 0.60gTi3·3H2O、Sr(OAC)2·0.5H2O、BeCl2、Cl3Sb、BiCl3, oxychloride hafnium
(HfOCl2·8H2) and ammonium titanium fluoride ((NH O4)2TiF6) be sufficiently mixed be dissolved in concentration be 8wt% aqueous hydrochloric acid solution in, obtain
Than surface it is 168m by 1.0L to maceration extract 400ml2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation exists
In above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are
6.50g/L, Sr content 1.60g/L, Be content 0.40g/L, Sb content 0.50g/L, Bi content 1.00g/L, Hf content is
1.20g/L, Ti content are 0.60g/L.
The synthesis of 3- acetoxyl group propionic aldehyde：By 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed 3- acetoxyl group propionic aldehyde is 90.36%, and selectivity is 98.25%, for convenience of description and is compared
Compared with preparation condition, reaction condition, material inlet amount, the yield of 3- acetoxyl group propionic aldehyde and the selectivity of catalyst are listed in respectively
Tables 1 and 2.
Found out on year-on-year basis by embodiment 18 and embodiment 16 and embodiment 17, improving the selectivity of 3- acetoxyl group propionic aldehyde
In terms of yield, in the catalyst that uses of the present invention, there is synergy between alkaline-earth metal Sr, Be, illustrate Rh, Sr, Be,
Synergy well between seven kinds of active components of Sb, Bi, Ti and Hf be present.
Table 1
Table 2 (continued)
The (Continued) of table 2
Claims (8)
1. the catalyst for synthesizing 3- acetoxyl group propionic aldehyde, the catalyst use SiO2、Al2O3Or its mixture is load
Body, active component include rhodium, alkaline-earth metal and selected from least one of VA and IVB metallic elements；The content of rhodium in catalyst
For 3.00~15.00g/L, the content of alkaline-earth metal is 0.10~3.00g/L；At least one of metal contains in VA and IVB
Measure as 0.10~5.00g/L.
2. catalyst according to claim 1, it is characterised in that the alkaline-earth metal in beryllium, magnesium, calcium, strontium and barium extremely
Few one kind.
3. catalyst according to claim 1, it is characterised in that the VA metals are selected from least one of antimony and bismuth.
4. catalyst according to claim 1, it is characterised in that the IVB metals are selected from least one of titanium, zirconium and hafnium.
5. the production method of the catalyst described in claim 1, comprises the following steps：
1. by the composition of catalyst by the solution and carrier of metallic compound in rhodium compound, alkaline earth metal compound, VA and IVB
Mixing；
2. dry.
6. the production method of catalyst according to claim 5, it is characterized in that step 1. the rhodium compound be selected from rhodium acetate,
At least one of rhodium nitrate, radium chloride and rhodium sulfate.
The synthetic method of 7.3- acetoxyl group propionic aldehyde, using vinyl acetate, carbon monoxide and hydrogen as raw material, using toluene as solvent,
3- acetoxyl group propionic aldehyde is synthesized in the presence of catalyst any one of Claims 1 to 4 and accelerator.
8. synthetic method according to claim 7, it is characterised in that the accelerator is in pyridine and triphenyl phosphorus
It is at least one.
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| CN101534945A (en) * | 2006-10-26 | 2009-09-16 | 大野绿水株式会社 | Fluidized-bed catalyst for the production of acrylonitrile and process for the production of acrylonitrile |
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| CN101116816A (en) * | 2007-07-03 | 2008-02-06 | 中国石油大学(华东) | Method for preparing load type rhodium catalyst for making high-carbon aldehyde using hydroformylation of higher olefins |
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